Method for treating and upgrading effluents containing metallic sulphates using an ammonia addition step

ABSTRACT

The invention concerns a method for treating and upgrading effluents containing at least a metallic sulphate, characterised in that it comprises steps which consist in: adding at least a base to the effluent to precipitate the metallic ions in the form of metallic hydroxides Me a (OH) e ; separating the precipitated hydroxide calcium sulphate CaSO 4 ; and separating the calcium sulphate CaSO 4  precipitated during the preceding step. Said method enables to obtain calcium sulphate (white gypsum) substantially free of metals and therefore capable of being upgrade and metallic oxy-hydroxides likewise capable of being upgraded.

[0001] This invention relates to the domain of the treatment of industrial effluents.

[0002] More precisely, this invention relates to treatment of liquid effluents containing mainly metallic sulphates and that can also contain sulphuric acid (H₂SO₄)

[0003] This type of effluents must be treated to give pure effluents that can be disposed of into the natural environment. In the past, the treatment designed to purify this type of effluents containing metallic sulphates consisted of adding calcium hydroxide Ca(OH)₂ to them to obtain a precipitate of calcium sulphate CaSO₄, 2H₂O, in other words gypsum.

[0004] However, this type of process has the major disadvantage that it also causes precipitation of metals originating from metallic sulphates in the form of metallic hydroxides Me_(a)(OH)_(e).

[0005] There are two problems in using these compounds which are obtained in a mixture with gypsum.

[0006] Firstly, the content of polluting metals in the gypsum makes it very difficult to upgrade the gypsum, taking account of the very low imposed metal concentration thresholds at the entry to recycling systems.

[0007] There is also the problem of possible coloration by metallic gypsum hydroxides, which are white in the pure state, that compromises upgrades of gypsum for which the whiteness index is a key factor.

[0008] In other words, the gypsum obtained at the end of this process cannot be used in industry and must be put into a tip. Consequently, the pollution will simply be displaced from the liquid effluent to a solid residue.

[0009] The purpose of this invention is to present a process for the treatment of industrial effluents containing metallic sulphates with or without sulphuric acid and that does not have the disadvantages of the process according to the state of the art described above.

[0010] In particular, one purpose of this invention is to describe such a process that can produce upgradeable products, in other words products that can usefully be used later in industry.

[0011] As a corollary, one purpose of this invention is to present such a process that can significantly reduce quantities of final residues to be stored in the tip.

[0012] Yet another purpose of the invention is to propose such a process that can be used without involving a high additional cost compared with the process according to prior art.

[0013] These various processes are achieved according to the invention that relates to an effluent treatment process containing at least one metallic sulphate, the said process being characterised in that it comprises steps that consist of:

[0014] adding a solution of ammonia NH₃ to the said effluent to obtain ammonium sulphate (NH₄)₂SO₄ in solution and a precipitation of metallic hydroxides Me_(a)(OH)_(e); the addition of ammonia enables basification of the effluent to give pH values between 7 and 9.5;

[0015] separate the metallic phase Me_(a)(OH)_(e) precipitated during the previous step from the rest of the effluent;

[0016] add calcium hydroxide Ca(OH)₂ to the said effluent to make the sulphates in solution precipitate in the form of hydrated calcium sulphate CaSO4; the added quantity of Ca(OH)₂ satisfying the stoechiometric reaction for the formation of calcium sulphate;

[0017] separate the hydrated calcium sulphate CaSO₄ precipitated during the previous step from the rest of the effluent; the residue may be washed and upgraded.

[0018] Therefore, the invention recommends that metals contained in the metallic sulphates should be precipitated by using a neutralization step, and then the metallic oxy-hydroxides thus precipitated should be separated from the rest of the effluent before precipitating the sulphates in the form of calcium sulphate and separating this calcium sulphate from the rest of the effluent. All these steps are carried out without addition of heat, with reaction temperatures of between 10° and 50° C.

[0019] By proceeding according to this method, the recovered calcium sulphate is not polluted by metallic phases. Thus, it has a whitish colour corresponding to its natural colour that makes it upgradeable in the different types of industry, particularly in the cement or plaster industry.

[0020] The process according to the invention is also a means of obtaining precipitated metallic oxy-hydroxides that can also be upgraded, in other words usefully used in industry and particularly in steelworks.

[0021] The following chemical reaction occurs when ammonia is added to the effluent:

Me_(a)(SO₄)_(b)+2bNH₃ +dH₂O->Me_(a)(OH)_(e)+2bNH₄ ⁺ +bSO₄ ²⁻

[0022] When calcium hydroxide Ca(OH)₂ is added, the CaSO₄ compound is partially precipitated according to the following reaction:

2NH₄ ⁺+SO₄ ²⁻ ₊Ca(OH)₂->CaSO₄, 2H₂O+2NH₃

[0023] According to one particularly attractive preferred variant of the invention, the ammonia NH₃ formed in this reaction is stripped or distilled so that the effluent can be separated and purified from this compound.

[0024] According to a preferred variant of the invention, the ammonia NH₃ recovered after this stripping or this distillation is then rerouted to the beginning of the process so that it can be used in the step mentioned above for precipitation of metals in the form of metallic oxy-hydroxides Me_(a)(OH)_(e).

[0025] In order to improve the efficiency of the process, the process preferably includes a preliminary step designed to increase the pH of the effluent so that it has a pH of about 2. Raw effluents containing metallic sulphates may also contain an acid such that they have a very acid pH less than 2 that can damage the reactional equilibrium. This type of preliminary neutralization step may be carried out in different ways known to an expert in the subject.

[0026] Advantageously, it will be noted that the steps to add alkaline nitrogenous compounds and calcium carbonate or hydroxide are advantageously carried out while stirring.

[0027] Furthermore, for better application of the process, a metal concentration in the effluent at the beginning of the process should be between 3 g/l and 120 g/l.

[0028] In conclusion, compared with prior art, the process according to the invention can be used to obtain two upgradeable by-products, namely firstly white gypsum CaSO₄, 2H₂O, and secondly Me_(a)(OH)_(e), instead of a non-upgradeable mix of these two compounds.

[0029] The invention and its various advantages will be more easily understood after reading the following description of the embodiment with reference to the single FIGURE.

[0030] According to this embodiment, an industrial effluent with the following composition of metals and a pH close to 2.5 and a temperature of 20° C. is added into a tank 1: Al: 360 mg/l Fe: 7600 mg/l Na: 300 mg/l Zn: 15 mg/l Mn: 590 mg/l K: 70 mg/l Ca: 500 mg/l V: 79 mg/l Mg: 450 mg/l SO₄: 20200 mg/l Cr: 23 mg/l Cd: 0.7 mg/l Cu: 1.6 mg/l Ni: 0.8 mg/l Pb: 0.9 mg/l

[0031] 25 ml of ammonia (NH₃) at 16.6 mol/l is added per litre of effluent, which corresponds to an NH₃/Fe molar ratio of about 3 and a pH of the effluent of about 9.5.

[0032] The following chemical reactions occur:

Fe²⁺ +bSO₄ ²⁻+2NH₃+2H₂O->Fe (OH)₂+2NH₄ ⁺ +bSO₄ ²⁻

Fe³⁺ +bSO₄ ²⁻+3NH₃+3H₂O->Fe(OH)₃+3NH₄ ⁺ +bSO₄ ²⁻

[0033] giving the following general reaction:

Fe^(x++) +bSO₄ ²⁻ +cNH₃ +dH₂O ->Fe(OH)_(x) +cNH₄ ⁺ +bSO₄ ²⁻

[0034] This reaction leads to the precipitation of mainly iron oxy-hydroxide Fe(OH)_(x).

[0035] After _ to 2 h of stirring using stirring means 2, the mix is filtered using filtration means 3. The analysis of the filtrate (filtrate 1) and the dry residue gives the following results:

[0036] Composition of Filtrate 1: Al: 0.5 mg/l Fe: <0.1 mg/l Na: 248 mg/l Zn: 1.2 mg/l Mn: 1.0 mg/l K: 65 mg/l Ca: 450 mg/l V: 0.3 mg/l Mg: 300 mg/l SO₄: 20100 mg/l Cr: 0.06 mg/l Cd: <0.05 mg/l Cu: 0.5 mg/l Ni: 0.6 mg/l Pb: <0.05 mg/l

[0037] Elementary Composition of the Metallic Residue: Al: 11.4 g/kg Fe: 461 g/kg S: 22.0 g/kg of D.M. of D.M. of D.M. Zn: 0.63 g/kg Mn: 24.0 g/kg K: 0.20 g/kg of D.M. of D.M. of D.M. Ca: 3.0 g/kg V: 4.2 g/kg Mg: 2.2 g/kg of D.M. of D.M. of D.M. Cu: 0.2 g/kg Cr: 1.3 g/kg of D.M. of D.M.

[0038] Filtrate 1 is then transferred into a tank 4 in which 88 ml of milk of lime at 200 mg/l is added, per litre of filtrate 1. The mix is then stirred for _ h using stirring means 5 and is then filtered using filtration means 6 to recover a filtrate (filtrate 2) and a precipitate of white gypsum (calcium sulphate).

[0039] The following reaction occurs:

2NH₄ ⁺+SO₄ ²⁻+Ca(OH)₂->CaSO₄, 2H₂O+2NH₃

[0040] The analysis of filtrate 2 and white gypsum gives the following results:

[0041] Composition of Filtrate 2: Al: 0.4 mg/l Fe: <0.1 mg/l Na: 180 mg/l Zn: 0.5 mg/l Mn: <0.1 mg/l K: 41 mg/l Ca: 880 mg/l V: <0.1 mg/l Mg: 0.1 mg/l SO₄: 1200 mg/l Cr: 0.05 mg/l Cd: <0.05 mg/l Cu: 0.15 mg/l Ni: 0.2 mg/l Pb: <0.05 mg/l

[0042] Composition of Gypsum: Fe: 0.42 g/kg of D.M. S: 174 g/kg of D.M. Zn: 0.29 g/kg of D.M. Al: 2.1 g/kg of D.M. Ca: 232 g/kg of D.M. Mg: 18 g/kg of D.M.

[0043] The gypsum obtained is almost pure and has very little metallic residues. Therefore, it may easily be upgraded.

[0044] The filtrate 2 is then stripped or distilled in a reactor 7 to recover the ammonia that is returned to the beginning of the installation.

[0045] The embodiment of the invention described herein is not intended to limit the scope of the invention. Therefore, many modifications can be made to it without going outside the scope of the invention. 

1. Process for the treatment of effluents containing at least one metallic sulphate, this process being characterised in that it comprises steps that consist of: adding a solution of ammonia NH₃ to the said effluent to obtain ammonium sulphate (NH₄)₂SO₄ in solution and a precipitation of metallic oxy-hydroxides Me_(a)(OH)_(e); the addition of ammonia enables basification of the effluent to give pH values between 7 and 9.5; separate the metallic phase Me_(a)(OH)_(e) precipitated during the previous step from the rest of the effluent; add calcium hydroxide Ca(OH)₂ to the said effluent to make the sulphates in solution precipitate in the form of hydrated calcium sulphate CaSO₄; the added quantity of Ca(OH)₂ satisfying the stoechiometric reaction for the formation of calcium sulphate; separate the hydrated calcium sulphate CaSO₄ precipitated during the previous step from the rest of the effluent; the residue may be washed and upgraded.
 2. Process according to claim 1, characterised in that it comprises an additional step for stripping or distillation of ammonia NH₃ formed during the precipitation of sulphates.
 3. Process according to claim 2, characterised in that it consists of rerouting the ammonia derived from the said stripping or distillation step to the said step leading to the precipitation of metallic oxy-hydroxides Me_(a)(OH)_(e).
 4. Process according to any one of claims 1 to 3, characterised in that it comprises a preliminary effluent neutralization step so that its pH is more than
 2. 5. Process according to any one of claims 1 to 4, characterised in that the said steps for the addition of ammonia and for the addition of calcium hydroxide are made while stirring, all these steps being done without any heat addition, with reaction temperatures preferably between 10° C. and 50° C.
 6. Process according to any one of claims 1 to 5, characterised in that a metal concentration of the said effluent is between 3 and 120 g/l at the beginning of the process.
 7. Process according to one of claims 1 to 6, characterised in that the said effluent contains metallic sulphates. 